EP1742996A1 - Compositions elastomeres plastiques - Google Patents

Compositions elastomeres plastiques

Info

Publication number
EP1742996A1
EP1742996A1 EP05743421A EP05743421A EP1742996A1 EP 1742996 A1 EP1742996 A1 EP 1742996A1 EP 05743421 A EP05743421 A EP 05743421A EP 05743421 A EP05743421 A EP 05743421A EP 1742996 A1 EP1742996 A1 EP 1742996A1
Authority
EP
European Patent Office
Prior art keywords
plasto
cross
fillers
composition according
elastomeric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05743421A
Other languages
German (de)
English (en)
Inventor
Italo Carfagnini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SoFTer SpA
Original Assignee
SoFTer SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SoFTer SpA filed Critical SoFTer SpA
Publication of EP1742996A1 publication Critical patent/EP1742996A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/04—Crosslinking with phenolic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the present invention relates to plasto-elastomeric compositions basically consisting of EPDM terpolymers and polyolefins with fillers of mineral origin.
  • the present invention extends the properties of a material with the trade name Forprene®, which is a compound of thermoplastic elastomers comprising a mixture of vulcanised olefinic rubber and polyolef ⁇ nic resin.
  • Forprene® is a compound of thermoplastic elastomers comprising a mixture of vulcanised olefinic rubber and polyolef ⁇ nic resin.
  • the basic composition of Forprene® is produced with a predetermined specific gravity, giving the end product characteristics which allow its use in different applications with a significant reduction in costs and the possibility of presenting a product with new characteristics that could not be achieved until now.
  • composition according to this invention comprises elastomeric polymers, plastomeric polymers, fillers of mineral origin, various additives and oil in different percentages according to the uses and depending on the desired result.
  • the present invention can be applied in the industrial sector in the production of chemical products, in particular polymer alloy-based products.
  • thermoplastic compositions consisting of resins and EPDM terpolymer elastomers
  • the cross-link agents used are a halogenated phenolic resin or a non-halogenated phenolic resin associated with halogen donors.
  • patent US 4.477.631 suggests associating the non- halogenated phenolic resin with metal oxides or metal carbonates.
  • Elastomer vulcanisation techniques are also known which use the dynamic cross-linking system, for example as described in US 3.884.882 in which the elastomeric copolymers are grafted beforehand with maleic anhydride to cross-link them and make them more compatible with plastomeric materials.
  • the use and study of known materials for the production of plasto- elastomeric compositions containing the elastomeric parts cross-linked by dynamic cross-linking by the cross-linking agents normally used in the rubber industry has involved several problems.
  • the non-halogenated phenolic resin used for cross-linking is an alkylphenol - formaldehyde resin, considering that, in addition to the non-halogenated phenolic resin, it was essential to use an aromatic carboxylic acid for cross-linking, in particular salicylic acid.
  • the non-halogenated phenolic resin used for cross-linking is a alkylphenol formaldehyde resin with the following general formula:
  • Mi and M2 are -CH2- or -CH 2 -C-CH2- radicals, which may be the same or different, Z is an alkylene, acrylic or alkyl radical containing between 4 and 16 carbon atoms, and n is an integer between 0 and 6.
  • the phenolic resin that can be used in the process according to said European patent is a resole resin of the phenol - formaldehyde type with the formula: OH
  • the vulcanisation system used therefore consists of a combination of an alkylphenol - formaldehyde type resin, preferably phenol - formaldehyde resole resin, with salicylic acid, where for each part of resin, measured by weight, between 0.1 and 0.8 parts salicylic acid is used, again measured by weight.
  • the process for preparing plasto-elastomeric compositions therefore consists in particular of subjecting to mastication with apparatuses designed for the plastics and/or rubbers sector, such as Banbury type internal mixers, compounding screws, roller mixers, Buss type mixers, etc., mixtures with 10 - 80% of their weight formed by EPDM terpolymer (consisting of at least two -olefinic monomers and at least one dienic monomer) in the presence of a cross-linking system with 0.5 - 15 parts by weight for every 100 parts of EPDM, of a non-halogenated phenolic resin and of salicylic acid in a weight ratio with said resin of between 0.1/1 and 0.8/1.
  • apparatuses designed for the plastics and/or rubbers sector such as Banbury type internal mixers, compounding screws, roller mixers, Buss type mixers, etc.
  • EPDM terpolymer consisting of at least two -olefinic monomers and at least one dienic monomer
  • Preparation takes place at a temperature equal to or higher than (preferably higher than) the "melting" point of the olefinic thermoplastic used and for a time sufficient to obtain a homogeneous mixture and partial or full (preferably full) cross- linking of the EPDM rubber part contained in the mixture.
  • This operation may be performed in a single compounding machine such as those indicated above, or in several machines positioned in a logical sequence (for example: Banbury + extruder, or turbo mixer “dry” mixer and twin screw extruder, Banbury + Buss, etc.).
  • This system allows a fine dispersion of the cross-linked EPDM elastomer to be obtained (non-discrete phase) within the "melted" plastomeric component (discrete phase) and with the cross-linked elastomer in the form of tiny spheroidal particles with a diameter of between 0.1 and 1.5 microns. Operations are preferably performed at temperatures of between 160 and 240°
  • C and the duration of mastication depends on the following factors: a) the degree of cross-linking to be impa ted to the EPDM elastomer contained in the composition; b) the quantity, as a % of the weight, of diene present in the EPDM elastomer polymeric chain; c) the weight quantity of the two above-mentioned cross-linking agents (phenolic resin + salicylic acid).
  • the basic components of the compositions the following must also be added:
  • the degree of EPDM cross-linking this is between 10 and 100% by weight of the total quantity present in the composition.
  • the weight is preferably between 50 and 98%.
  • the amount of diene present in the EPDM elastomer is defined by the degree of non-saturation and is normally expressed by the quantity, by weight, of diene for every 100 parts, by weight, of elastomer; this value varies between 1 and 15% by weight, the EPDM elastomers preferably containing between 3 and 8% by weight of diene for the total EPDM elastomer.
  • the quantities of phenolic resin to be used for dynamic cross-linking of the EPDM elastomer are between 0.5 and 15 parts by weight per 100 parts of EPDM by weight, whilst between 0.05 and 12 pats by weight of salicylic acid is used per 100 parts of EPDM by weight.
  • organic strengthening ingredients e.g.: carbon black
  • inorganic ingredients e.g.: silica, silicates
  • plasticisers e.g.: mineral oils, waxes, paraffins
  • fillers inert fillers such as carbonates, kaolins, talc, calcined clay, barytes, asbestos, etc.
  • antioxidants antiozonants, anti UN., peptizing and anti-packing agents, organic and inorganic pigments, vulcanisation promoters.
  • EPDM terpolymers refers to mainly amorphous polymers consisting of ethylene and of at least one ⁇ -olefin (propylene, butene-1) and of a type of diene conjugated or not conjugated in the main polymeric chain and consisting of: ethylidene-norbornene; 1 ,4-hexadiene; dicyclopentadiene; 2-methyl-l,4-pentadiene; 1 ,4,9-decatriene; 1,5-cyclooctadiene; l-methyl-l ,5-cyclooctadiene; 1 ,4- cyclopentadiene; polyb ⁇ tene, polybutadiene and the substitution derivatives of such monomers.
  • They have a molecular weight of between 50,000 and 800,000: an ethylene content of between 20 and 80% in moles, a bound diene content of between 1 and 15% by weight per 100 parts of polymer by weight and the remainder consists of a propylene or butylene ⁇ -olefin.
  • olef ⁇ nic plastomers is used herein to refer to the products of copolymerisation of olef ⁇ nic monomers such as: ethylene; propylene; 1-butene; 1-pentene; 1-hexene, 4-methyl-l-pentene; 3- methyl-1-lpentene, 3,3-dimethyl-l-butene; ' 3 -methyl- 1-hexene; 2,4,4-trimethyl-l- pentene.
  • phenolic resins defined by the general formula indicated above, refers to those resins which may be prepared by the condensation of alkyl-phenols with formic aldehyde for example as described in literature (Kunstscher Vol. 52, 1962, pages 19 to 21).
  • the compositions according to European patent EP-B- 230212 are marketed with the name Forprene®.
  • the invention aims to. provide a polymeric formulation for plasto-elastomeric compositions based on dynamically cross-linked EPDM terpolymers and polyolefins, which is easy to produce so that it is economically advantageous. Moreover, the invention aims to provide a plasto-elastomeric composition based on EPDM terpolymers and polyolefins which can be used in different applications, for example: - sound-deadening panels; - extruded profiles; satinised surfaces; - low shrinkage materials; - applications requiring a specific gravity well above that of water; - halogen-free flame-proof compositions; - compositions for filling synthetic football fields.
  • a plasto-elastomeric composition based on EPDM terpolymers and polyolefins whose characteristics are described in the main claim.
  • the dependent claims of the polymeric formation disclosed refer to advantageous embodiments of the invention.
  • the end product made using such a composition also has the advantage of being recyclable, and costing less than other materials such as polyurethane.
  • the product may be defined recyclable, environmentally friendly and non- toxic, since it does not release toxic substances into the environment, and it is also free of heavy metals in compliance with current legislation, it does not produce dusts and is resistant to ageing.
  • Other, features and advantages of the invention are apparent in the following description of a preferred embodiment of the invention, by way of example and without limiting the scope of the inventive concept.
  • Production of the formulation according to this invention involves the initial preparation of .
  • a composition based on a mixture of vulcanised olef ⁇ nic resin and polyolefmic resin.
  • such a composition is known with the brand name Forprene®.
  • Fillers of mineral origin are added to said basic composition to reach a total specific gravity of around 2 kg/dm 3 , for a quantity which reaches up to a value close to 90% by weight, and with hardnesses ranging from ShA 40 to ShD 50.
  • the fillers of mineral origin may consists of the following components: - Calcium carbonate (coated and uncoated); - aluminium hydroxide; - magnesium hydroxide; - Barytes.
  • the calcium carbonate - chemical formula CaCo 3 - may or may not be pure, precipitated or not, and its specific gravity is 2.71 g/cm 3 .
  • the aluminium hydroxide - chemical formula Al(OH) 3 - has a typical specific gravity of 2.42 g/cm 3 and usually begins decomposing at 180°C, finishing at 320°C.
  • the magnesium hydroxide - chemical formula Mg(OH) 2 - typically begins decomposing at 300°C and finishes at 450°C.
  • Barytes - chemical formula BaSO 4 - is a more or less pure barium sulphate with different colours depending on where it is extracted and a typical specific gravity of 4.48 g/cm , which is a high value for a non-metallic mineral.
  • the addition of these fillers of mineral origin to the Forprene® allows the creation of a composition suitable for various applications, to prepare manufactured products which may be identified, without in any way limiting them, by the following: sound-deadening panels, extruded profiles, satinised surfaces, low shrinkage materials, applications requiring a specific gravity well below that of water.
  • compositions with marked flame-proof characteristics, to the point that with regard to the UL 94 classification, the composition can exceed NO product coding.
  • This type of composition may be used for filling synthetic football fields or for sports fields and equipment in general.
  • the capacity of the composition according to this invention to incorporate a high percentage of fillers of mineral origin, up to 90%, means that it can be used as a product suitable for filling football fields made of synthetic grass. It behaves similarly to vulcanised crumb rubber but without having the latter' s disadvantages in terms of pollution of the ground below, packing, smell, and above all no recycling.
  • Forme® is a dynamically cross-linked EPDM mixed with a homo or copo polypropylene and polyethylene LDPE/LLDPE/HDPE, making it perfectly recyclable.
  • the basic composition of Forprene® is preferably vulcanised
  • Table 3 corresponds to a composition for filling synthetic football fields:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition élastomère plastique à base de terpolymère EPDM et de polyoléfine contenant une phase élastomère partiellement ou complètement réticulée, pour la réticulation de laquelle on peut utiliser une résine alkylphénol-formaldéhyde non halogénée ou une résine résole phénol-formaldéhyde non halogénée, un acide carboxylique aromatique étant utilisé pour la réticulation, en particulier un acide salicylique, des charges d'origine minérale étant ajoutées, soit directement au cours de l'étape de mélange au moment de la réticulation, ou par la suite au matériau déjà réticulé, afin d'obtenir une densité totale allant jusqu'à 2 kg/dm3 avec une dureté comprise entre 40 ShA et 50 ShD. Les charges d'origine minérale peuvent atteindre une quantité de presque 90 % en poids de la composition.
EP05743421A 2004-05-03 2005-04-21 Compositions elastomeres plastiques Withdrawn EP1742996A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000074A ITVR20040074A1 (it) 2004-05-03 2004-05-03 Composizioni plasto-elastomeriche a base di poliolefine e terpolimeri epdm addizionate di cariche minerali.
PCT/IT2005/000236 WO2005105915A1 (fr) 2004-05-03 2005-04-21 Compositions elastomeres plastiques

Publications (1)

Publication Number Publication Date
EP1742996A1 true EP1742996A1 (fr) 2007-01-17

Family

ID=34968172

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05743421A Withdrawn EP1742996A1 (fr) 2004-05-03 2005-04-21 Compositions elastomeres plastiques

Country Status (4)

Country Link
US (1) US20070072999A1 (fr)
EP (1) EP1742996A1 (fr)
IT (1) ITVR20040074A1 (fr)
WO (1) WO2005105915A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014111691A (ja) * 2012-12-05 2014-06-19 Sumitomo Rubber Ind Ltd 熱可塑性エラストマ組成物
JP6378533B2 (ja) * 2013-06-01 2018-08-22 日東電工株式会社 熱伝導性粘着シート

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617377A (en) * 1966-06-10 1971-11-02 Fujikura Ltd Insulation consisting of ethylene-propylene rubber composition for electric wire and cable
IT1193549B (it) * 1980-08-19 1988-07-08 Montedison Spa Procedimento per la preparazione di composizioni plasto-elastomeriche poliolefiniche,mediante vulcanizzazione dinamica
IT1203607B (it) * 1985-12-20 1989-02-15 So F Ter Spa Procedimento per preparare composizioni plasto-elastomeriche a base di poliolefine e terpolimeri epdm e le composizioni plasto-elastomeriche cosi' ottenute
IT1223262B (it) * 1987-12-11 1990-09-19 Himont Inc Composizioni elasto plastiche e procedimento per la loro preparazione
EP0405982A1 (fr) * 1989-06-28 1991-01-02 Nippon Petrochemicals Company, Limited Composition de résine thermoplastique contenant une charge
ATE136568T1 (de) * 1990-06-12 1996-04-15 Advanced Elastomer Systems Thermoplastische elastomerzusammensetzung
IT1256734B (it) * 1992-12-17 1995-12-15 Paranova Articoli Tecnici Procedimento per la preparazione di composizioni plasto-elastomeriche di natura poliolefinica mediante vulcanizzazione dinamica con resina alchilfenolo-formaldeide e bisolfito di sodio.
US5952425A (en) * 1996-12-31 1999-09-14 Advanced Elastomer Systems, L.P. Preferred structure of phenolic resin curative for thermoplastic vulcanizate
US7074137B2 (en) * 1997-10-03 2006-07-11 Acushnet Company Golf ball
US5990204A (en) * 1997-10-31 1999-11-23 Onizawa; Masao Crosslinking isoprene-isobutylene rubber with alkyphenol-formaldehyde and epoxy resins
JP2002302581A (ja) * 2001-04-04 2002-10-18 Kinugawa Rubber Ind Co Ltd 遮音性複合材組成物および遮音カバー部材

Non-Patent Citations (1)

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Title
See references of WO2005105915A1 *

Also Published As

Publication number Publication date
ITVR20040074A1 (it) 2004-08-03
WO2005105915A1 (fr) 2005-11-10
US20070072999A1 (en) 2007-03-29

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